Microwave dielectric ceramic composition

ABSTRACT

Disclosed herein is a microwave dielectric ceramic composition which comprises as the main ingredient, a composition represented by xMgTiO 3  ·(1-x)CaTiO 3  (0.93≦x ≦0.95), to which 3-9 wt % of ZnO, 2-4 wt % of Ta 2  O 5 , 1-6 wt % of Nb 2  O 5 , 0.1-6 wt % of MnO 2 , 3-12 wt % of Al 2  O 3  or 3-12 wt % of Co 2  O 3  to xMgTiO 3  ·(1-x)CaTiO 3 . And the microwave dielectric ceramic compositions have a Qu value in the range of 3000 to 4600 (at 6 GHz), a temperature coefficient of the resonance frequency (τf) in the range of -10 to +10 ppm/°C. and relative dielectric constant (ε r ) in the range of 18 to 22. The dielectric ceramic compositions are capable of reducing τf approximately to zero or optionally and stably controlling τf to a desired value both to positive and negative sides around zero as the center while maintaining ε r  and Qu within practical characteristic ranges by controlling the addition (constitution) ratio of the specified oxides. Further, even if the sintering temperature is changed within a wide range, the sintering products of high density and high quality can be attained due to the addition of the specified oxides.

BACKGROUND OF THE INVENTION

The present invention concerns a microwave dielectric ceramic composition and, more specifically, it relates to a microwave dielectric ceramic composition capable of reducing a temperature coefficient of a resonance frequency (hereinafter simply referred to as τf) while maintaining non-load Q (hereinafter simply referred to as Qu) and, further, capable of optionally controlling τf to positive and negative sides around zero as the center by controlling the mixing ratio of CaTiO₃ or a specified oxide. The present invention also relates to a microwave dielectric ceramic composition and having high quality even if it is sintered at a low temperature due to the addition of a specified oxide or with less scattering in the quality even if it is sintered in a wide temperature range.

The present invention is applicable to impedance matching or the like of dielectric resonators, microwave integrated circuit boards and various kinds of microwave circuits in a microwave region.

Since the dielectric loss of a microwave dielectric ceramic composition (hereinafter simply referred to as a dielectric ceramic composition) tends to increase as the working frequency goes higher, a dielectric ceramic composition of high Qu in a microwave frequency region has been demanded.

As conventional dielectric ceramic materials, a dielectric ceramic composition of a crystal structure containing two phases, that is, a perovskite phase and an ilmenite phase (Japanese Patent Laid-Open Hei 2-129065) and a dielectric ceramic composition containing a predetermined amount of CaTiO₃ in MgTiO₃ and TiO₂ (Japanese Patent Laid-Open Sho 52-118599) have been known.

However, the former dielectric ceramic composition obtained other ingredients such as Nd₂ O₃, La₂ O₃, PbO, ZnO in a great amount and, in addition, the value Qu is not always high. The latter dielectric ceramic composition contains TiO₂ as the essential ingredient and τf changes greatly as from +87 to -100 within a range for the mixing amount of CaTiO₃ from 3 to 10% by weight to bring about a problem such as a difficulty for the control to a small value around zero.

The present invention intends to solve the foregoing problem and it is an object of the present invention to provide a dielectric ceramic composition capable of reducing τf approximately to zero or optionally and stably controlling τf to a desired value both to positive and negative sides around zero as the center while maintaining ε_(r) (relative dielectric constant) and Qu within practical characteristic ranges by controlling the addition (constitution) ratio of specified oxides (ZnO, Ta₂ O₅, Nb₂ O₅, MnO₂, Al₂ O₃ or Co₂ O₃) and, further, having a high quality even if it is sintered at a low temperature or even if it is sintered in a wide temperature range due to the addition of a specified oxide.

SUMMARY OF THE INVENTION

The present inventor has made various studies on a composition of a dielectric ceramic composition capable of approaching τf to zero while maintaining a high Qu value and having stable quality even if sintering temperature varies and, as a result, has accomplished the present invention based on the finding that the foregoing drawback can be overcome by adjusting the addition ratio of CaTiO₃ and specified oxide.

Namely, the dielectric ceramic composition according to the present invention comprises, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ (0.925≦x≦0.950), to which 3 to 9 parts by weight (hereinafter referred to as % by weight) of ZnO is added and incorporated based on 100 parts by weight of xMgTiOa·(1-x)CaTiO₃.

If x is smaller than 0.925, τf takes a large positive value and Qu is lowered, whereas τf takes a large negative value if x exceeds 0.950, which are not preferred. In particular, it is preferred that x is from 0.935 to 0.945 and the addition amount of ZnO is 6% by weight, since Qu is from 3900 to 4100, τf is -5 to +5 (ppm/°C.) and ε_(r) is about 21, high quality can be ensured even by sintering at a low temperature and stability to the sintering temperature is obtained.

As the mixing ratio of CaTiO₃ increases, τf increases from negative to positive side (FIG. 3) and ε_(r) increases (FIG. 2), while Qu tends to decrease (FIG. 1). Further, as shown in FIG. 7, a sintering product of high density can be produced even by sintering at a low temperature (for example, at 1325° to 1350° C.) and, accordingly, stable quality can be attained even if the sintering temperature changes variously (or even if sintering is conducted at a low temperature) (FIGS. 4-11).

In view of the above, within an appropriate mixing range for CaTiO₃ and ZnO described above, a balance is attained for the characteristics and stable quality can be obtained.

The dielectric ceramic composition according to another aspect of the present invention comprises, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x) CaTiO₃ (in which 0.923≦x≦0.940), to which 2 to 4 parts by weight (hereinafter referred to as % by weight) of Ta₂ O₅ is added and incorporated based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃.

If x is smaller than 0.923, τf takes a large positive value and Qu decreases, whereas if x exceeds 0.940, τf takes a large negative value, which are not preferred. Particularly, it is preferred that x is from 0.927 to 0.935 and the addition amount of Ta₂ O₅ is 3% by weight, since Qu is from 3920 to 4260, τf is from -8.5 to +2.3 (ppm/°C.), ε_(r) is from 19.7 to 21.6 and the scattering in the characteristics is extremely small even if sintering temperature is varied.

As the mixing ratio of CaTiO₃ increases, τf increases from negative to positive value (FIG. 16), ε_(r) increases (FIG. 15), while Qu tends to reduce (FIG. 14). Further, as shown in FIG. 23, sintering products at high density can be produced even if sintering is applied at a low temperature (for example, at 1300°-1325° C.) due to the addition of Ta₂ O₅. Further, products of stable quality can be obtained if the sintering temperature is varied within a range of 1300° to 1400° C. (FIGS. 17-23).

In view of the above, within the appropriate mixing range of CaTiO₃ and Ta₂ O₅ described above, the characteristics are well-balanced and products of stable quality can be obtained.

The dielectric ceramic composition according to other aspect of the present invention comprises, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x) CaTiO₃ (in which 0.925≦x≦0.940), to which 1 to 6 parts by weight (hereinafter referred to as % by weight) of Nb₂ O₅ is added and incorporated based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃.

If x is smaller than 0.925, τf takes a large positive value and Qu decreases, whereas τf takes a large negative value if x exceeds 0.940, which are not preferred. Particularly, it is preferred that x is 0.930 and the addition amount of Nb₂ O₅ is 2% by weight, since Qu is from 3980 to 4320 τf is from -3.69 to +0.52 ppm/°C. and ε_(r) is from 19.05 to 21.5 when sintering is applied at 1275°-1400° C., and products of high quality can be obtained stably even if sintering is applied within a wide temperature range.

As the mixing ratio of CaTiO₃ increases, τf increases from negative to positive value (FIG. 28), ε_(r) increases (FIG. 27), while Qu tends to decrease (FIG. 26). Further, as shown in FIGS. 29-31 although Qu and τf do not vary so much but τf tend to decrease due to the addition of Nb₂ O₅. Particularly, at the mixing ratio of CaTiO₃ of 0.07, the addition amount of Nb₂ O₅ of about 2% by weight is extremely preferred since τf is about 0 ppm/°C. Further, as shown in FIGS. 32-36 and Tables 5 and 6, sintering products of stable performance and high sintering density can be produced even if sintering is applied within a wide temperature range. Accordingly, addition amount of Nb₂ O₅, particularly, of 1 to 4% by weight, (more particularly, about 2% by weight) is excellent in view of further excellent balance of performance and stable sintering product.

In view of the above, within the appropriate mixing range of CaTiO₃ and Nb₂ O₅ described above, products of excellent performances with excellent balance and of stable quality can be obtained.

The dielectric ceramic composition according to other aspect of the present invention comprises, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ (in which 0.93≦x≦0.95), to which 0.1 to 6 parts by weight (hereinafter referred to as % by weight) of MnO₂ is added and incorporated based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃.

If x is smaller than 0.93, τf takes a large positive value and Qu decreases, whereas τf takes a large negative value if x exceeds 0.95, which are not preferred. Particularly, if x is 0.94 and the addition amount of MnO₂ is 3 to 6% by weight, Qu is from 3080 to 3890, τf is from -2.60 to +1.78 ppm/°C., and ε_(r) is from 19.04 to 20.95 when sintering is applied at 1350°-1425° C. as shown in Table 8, and products of high quality can be obtained even if sintering is applied within a wide temperature range. As the mixing ratio of CaTiO₃ increases, τf increases from negative to positive value (Table 7, FIGS. 40, 44, 48), ε_(r) increases (Table 7, FIGS. 39, 43, 47), while Qu tends to decrease (Table 7, FIGS. 38, 42 and 46). Further, in a case of adding MnO₂, Qu tends to decrease (FIG. 38), ε_(r) (within a range of 1375° to 1425° C.) shows no substantial change (FIG. 39), τf tends to decrease (FIGS. 40, 48) and the sintering density tends to increase (FIGS. 41, 49). Particularly, at the mixing ratio of CaTiO₃ is 0.06, the addition amount of MnO₂ of about 3% by weight is extremely preferred since τf is about 0 ppm/°C. even if the sintering temperature is greatly varied as 1325° to 1425° C. as shown in FIG. 40. Further, as shown in FIGS. 38-49 and Tables 8-10, sintering products with stable performance and high sintering density can be produced even if sintering is applied within a wide temperature range (particularly from 1375° to 1425° C.).

Further, in a case where the mixing ratio of CaTiO₃ is 0.05, τf is as small as about -10 ppm/°C. even within the range for the addition amount of MnO₂ from 0.1 to 0.6. On the other hand, in a case where the mixing ratio of CaTiO₃ is 0.07, τf is as large as +10 ppm/°C. within the addition amount range of MnO₂ of 3 to 6% by weight. Accordingly, the mixing ratio of CaTiO₃ of about 0.06 and the addition amount of MnO₂, particularly, of 1 to 6% by weight (more particularly, about 3% by weight) are more excellent in view of further excellent balance of performance and stable sinterability.

In view of the above, within the appropriate mixing range of CaTiO₃ and MnO₂ described above, products of excellent performance with well-balancing thereof and of stable quality can be obtained.

The dielectric ceramic composition according to other aspect of the present invention comprises, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ (in which 0.93≦x≦0.95), to which 3 to 12 parts by weight (hereinafter referred to as % by weight) of Al₂ O₃ is added and incorporated based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃.

If x is smaller than 0.93, τf takes a large positive value and Qu decreases, whereas τf takes a large negative value if x exceeds 0.95, which are not preferred.

As the addition amount of Al₂ O₃ increases Qu tends to increase (FIG. 51), and ε_(r), τf and the sintering density tend to decrease (FIGS. 52-54). Particularly, if the addition amount of Al₂ O₃ is 3 to 9% by weight and the sintering temperature is from 1300° to 1375° C., Qu is 3360 to 3730, ε_(r) is 18.4 to 20.6, τf is -2.2 to +2.6 ppm/°C., the sintering density is 3.57 to 3.82 g/cm³ as shown in Table 11 and FIGS. 51-54, and products of high quality can be obtained stably even if sintering is applied within a wide temperature range. Particularly, τf scarcely fractuates (namely, concentrating to -2-+3 ppm/°C.) and shows a value around 0 in each of the cases.

In view of the above, products of excellent performance described above and excellent balance thereof and of stable quality can be obtained by the addition amount of Al₂ O₃ (3-9% by weight) and in a wide and appropriate sintering temperature range (1300°-1375° C.).

The dielectric ceramic composition according to other aspect of the present invention comprises, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ (in which 0.93≦x≦0.95), to which 3 to 12 parts by weight (hereinafter referred to as % by weight) of Co₂ O₃ is added and incorporated based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃.

If x is smaller than 0.93, τf takes a large positive value and Qu decreases, whereas τf takes a large negative value if x exceeds 0.95, which are not preferred.

If the addition amount of Co₂ O₃ is less than 3% by weight, τf increases toward the positive side and Qu decreases if the addition amount exceeds 12% by weight, which are not preferred. On the other hand, if the addition amount is from 3 to 12% by weight, τf can be reduced to a value around zero while concentrating Qu and ε_(r) within practical ranges with no substantial reduction.

Then, as the mixing ratio of CaTiO₃ increases, it tends to decrease Qu, increase ε_(r) and turn τf from negative to positive value (Table 7). Further, as the addition amount of Co₂ O₃ increases, Qu tends to decrease (FIG. 64), ε_(r) tends to decrease slightly although shows no substantial change (FIG. 65), τf tends to turn to negative side (FIG. 66) and the sintering density tend to increase (FIG. 67).

Particularly, if the addition amount of Co₂ O₃ is 6 wt % and sintering is applied at 1350° to 1450° C., Qu is 3780 to 3970, τf is -0.74 to -0.03 ppm/°C., ε_(r) is 20.4 to 20.8 and the sintering density is 3.83 to 3.89 g/cm³ as shown in Table 12 and FIGS. 64-71, and each of the performances less scatters and excellent performances is exhibited even sintering is applied within a wide temperature range of 100° C. In particular, τf takes an extremely small absolute value around 0 ppm/°C. and shows a value of about 0.5 (ppm/°C.)/1 wt % of Co₂ O₃, and fine control for τf can be done extremely easily.

In view of the above, products having such excellent performance and well balance thereof, as well as capable of easy fine control for τf and of stable quality can be attained by the addition amount of Co₂ O₃ and in a wide and appropriate sintering temperature range.

As has been described above, in the dielectric ceramic composition according to the present invention, τf can be approached to zero or optionally controlled to a desired value between both of positive and negative sides around 0 (zero) as a center by controlling the blending ratio of CaTiO₃ while maintaining Qu and ε_(r) within practical (high) ranges of characteristics, as well as τf can be controlled stably around 0 (zero). Further, even if the sintering temperature is changed within a wide range, sintering products of high density and high quality can be attained due to the addition of ZnO₂, Ta₂ O₅, Nb₂ O₅, MnO₂, Al₂ O₃ or Co₂ O₃. In the case of adding ZnO, sintering products of high quality can be obtained even if sintering is applied at a relatively low temperature. Further, in a case of adding Co₂ O₃, τf can be finely controlled easily.

Accordingly, the mixing ratio of CaTiO₃ and specific oxides (ZnO and so on) can be varied depending on the purpose.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing a relation between x and Qu in a (xMgTiO₃ ·(1-x)CaTiO₃ +6 wt % ZnO) ceramic composition produced at a sintering temperature of 1350° C.

FIG. 2 is a graph showing a relation between x and ε_(r) in the ceramic composition shown in FIG. 1.

FIG. 3 is a graph showing a relation between x and τf in the ceramic composition shown in FIG. 1.

FIG. 4 is a graph showing a relation between the amount of ZnO and Qu in a (0.94MgTiO₃ ·0.06CaTiO₃ +(0-9) wt % ZnO) ceramic composition produced by sintering at each of sintering temperatures.

FIG. 5 is a graph showing a relation between the amount of ZnO and ε_(r) in the ceramic composition shown in FIG. 4.

FIG. 6 is a graph showing a relation between the amount of ZnO and τf in the ceramic composition shown in FIG. 4.

FIG. 7 is a graph showing a relation between the amount of ZnO and the sintering density in the ceramic composition shown in FIG. 4.

FIG. 8 is a graph showing a relation between the sintering temperature and Qu in the (0.94MgTiO₃ ·0.06CaTiO₃ +(0-9) wt % ZnO) ceramic composition.

FIG. 9 is a graph showing a relation between the sintering temperature and ε_(r) in the ceramic composition shown in FIG. 8.

FIG. 10 is a graph showing a relation between the sintering temperature and τf in the ceramic composition shown in FIG. 8.

FIG. 11 is a graph showing a relation between the sintering temperature and the sintering density in the ceramic composition shown in FIG. 8.

FIG. 12 is a graph showing the result of X-ray diffraction of a (0.95MgTiO₃ ·0.05CaTiO₃ +6 wt % ZnO) ceramic composition.

FIG. 13 is a graph showing the result of X-ray diffraction of a (0.95MgTiO₃ ·0.05CaTiO₃) ceramic composition.

FIG. 14 is a graph showing a relation between x and Qu in a (xMgTiO₃ ·(1-x)CaTiO₃ +3 wt % Ta₂ O₅) ceramic composition produced by sintering at each of sintering temperatures.

FIG. 15 is a graph showing a relation between x and ε_(r) in the ceramic composition shown in FIG. 14.

FIG. 16 is a graph showing a relation between x and τf in the ceramic composition shown in FIG. 14.

FIG. 17 is a graph showing a relation between the amount of Ta₂ O₅ and Qu in a (0.93MgTiO₃ ·0.07CaTiO₃ +(2-4) wt % Ta₂ O₅) ceramic composition produced by sintering at each of sintering temperatures.

FIG. 18 is a graph showing a relation between the amount of Ta₂ O₅ and ε_(r) in the ceramic composition shown in FIG. 17.

FIG. 19 is a graph showing a relation between the amount of Ta₂ O₅ and τf in the ceramic composition shown in FIG. 17.

FIG. 20 is a graph showing a relation between the sintering temperature and Qu in the (0.93MgTiO₃ ·0.07CaTiO₃ +(0-4) wt % Ta₂ O₅) ceramic composition.

FIG. 21 is a graph showing a relation between the sintering temperature and ε_(r) in the ceramic composition shown in FIG. 20.

FIG. 22 is a graph showing a relation between the sintering temperature and τf in the ceramic composition shown in FIG. 20.

FIG. 23 is a graph showing a relation between the sintering temperature and the sintering density in the ceramic composition shown in FIG. 20.

FIG. 24 is a graph showing the result of X-ray diffraction of a xMgTiO₃ ·(1-x)CaTiO₃ +3 wt % Ta₂ O₅, the sintering temperature: 1300° C.) ceramic composition.

FIG. 25 is a graph showing the result of X-ray diffraction of a xMgTiO₃ ·(1-x)CaTiO₃ +3 wt % Ta₂ O₅, the sintering temperature: 1350° C.) ceramic composition.

FIG. 26 is a graph showing a relation between x and Qu in a (xMgTiO₃ ·(1-x)CaTiO₃ +2 wt % Nb₂ O₅) ceramic composition produced by sintering at each of sintering temperatures.

FIG. 27 is a graph showing a relation between x and ε_(r) in the ceramic composition shown in FIG. 26.

FIG. 28 is a graph showing a relation between x and τf in the ceramic composition shown in FIG. 26.

FIG. 29 is a graph showing a relation between the amount of Nb₂ O₅ and Qu in a (0.93MgTiO₃ ·0.07CaTiO₃ +(0-6) wt % Nb₂ O₅) ceramic composition produced by sintering at each of sintering temperatures.

FIG. 30 is a graph showing a relation between the amount of Nb₂ O₅ and ε_(r) in the ceramic composition shown in FIG. 29.

FIG. 31 is a graph showing a relation between the amount of Nb₂ O₅ and τf in the ceramic composition shown in FIG. 29.

FIG. 32 is a graph showing a relation between the amount of (0-6 wt %) Nb₂ O₅ and the sintering density in the ceramic composition shown in FIG. 29.

FIG. 33 is a graph showing a relation between the sintering temperature and Qu in the (0.93MgTiO₃ ·0.07CaTiO₃ +(1-6) wt % Nb₂ O₅) ceramic composition.

FIG. 34 is a graph showing a relation between the sintering temperature and ε_(r) in the ceramic composition shown in FIG. 33.

FIG. 35 is a graph showing a relation between the sintering temperature and τf in the ceramic composition shown in FIG. 33.

FIG. 36 is a graph showing a relation between the sintering temperature and the sintering density in the ceramic composition shown in FIG. 33.

FIG. 37 is a graph showing the result of X-ray diffraction of a (0.93MgTiO₃ ·0.07CaTiO₃ +(2, 4 or 6 wt %) Nb₂ O₅) ceramic composition.

FIG. 38 is a graph showing a relation between the amount of MnO₂ and Qu in a (0.94MgTiO₃ ·0.06CaTiO₃ +0-6 wt % MnO₂) ceramic composition produced by sintering at each of sintering temperatures.

FIG. 39 is a graph showing a relation between the amount of MnO₂ and ε_(r) in the ceramic composition shown in FIG. 38.

FIG. 40 is a graph showing a relation between the amount of MnO₂ and τf in the ceramic composition shown in FIG. 38.

FIG. 41 is a graph showing a relation between the amount of 0-6 wt % MnO₂ and the sintering density in the ceramic composition shown in FIG. 38.

FIG. 42 is a graph showing a relation between the sintering temperature and Qu in the (0.95MgTiO₃ ·0.05CaTiO₃ +(0-0.6) wt % MnO₂) ceramic composition.

FIG. 43 is a graph showing a relation between the sintering temperature and ε_(r) in the ceramic composition shown in FIG. 42.

FIG. 44 is a graph showing a relation between the sintering temperature and τf in the ceramic composition shown in FIG. 42.

FIG. 45 is a graph showing a relation between the sintering temperature and the sintering density in the ceramic composition shown in FIG. 42.

FIG. 46 is a graph showing a relation between the sintering temperature and Qu in the (0.93MgTiO₃ ·0.07CaTiO₃ +(0-6) wt % MnO₂) ceramic composition.

FIG. 47 is a graph showing a relation between the sintering temperature and ε_(r) in the ceramic composition shown in FIG. 46.

FIG. 48 is a graph showing a relation between the sintering temperature and τf in the ceramic composition shown in FIG. 46.

FIG. 49 is a graph showing a relation between the sintering temperature and the sintering density in the ceramic composition shown in FIG. 46.

FIG. 50 is a graph showing the result of X-ray diffraction of a (0.94MgTiO₃ ·0.06CaTiO₃ +(0, 3 or 6 wt %) MnO₂) ceramic composition.

FIG. 51 is a graph showing a relation between the amount of Al₂ O₃ and Qu in a (0.94MgTiO₃ ·0.06CaTiO₃ +0-12 wt % Al₂ O₃) ceramic composition produced by sintering at each of sintering temperatures.

FIG. 52 is a graph showing a relation between the amount of Al₂ O₃ and ε_(r) in the ceramic composition shown in FIG. 51.

FIG. 53 is a graph showing a relation between the amount of Al₂ O₃ and τf in the ceramic composition shown in FIG. 51.

FIG. 54 is a graph showing a relation between the amount of 3-12 wt % Al₂ O₃ and the sintering density in the ceramic composition shown in FIG. 51.

FIG. 55 is a graph showing a relation between the sintering temperature and Qu in the (0.94MgTiO₃ ·0.06CaTiO₃ +(3-12) wt % Al₂ O₃) ceramic composition.

FIG. 56 is a graph showing a relation between the sintering temperature and ε_(r) in the ceramic composition shown in FIG. 55.

FIG. 57 is a graph showing a relation between the sintering temperature and τf in the ceramic composition shown in FIG. 55.

FIG. 58 is a graph showing a relation between the sintering temperature and the sintering density in the ceramic composition shown in FIG. 55.

FIG. 59 is a graph showing a relation between the amount of Al₂ O₃ and the average grain size of sintering product in the (0.94MgTiO₃ ·0.06CaTiO₃ +3-12 wt % Al₂ O₃) ceramic composition produced at a sintering temperature of 1350° C.

FIG. 60 is a graph showing a relation between the sintering temperature and the average grain size of sintering product in the (0.94MgTiO₃ ·0.06CaTiO₃ +12 wt % Al₂ O₃) ceramic composition produced at a sintering temperature of 1350° C.

FIG. 61 is the electron microscopic photograph (1000 magnification ratio) which explains the structure of crystals of the (0.94MgTiO₃ ·0.06CaTiO₃ +6 wt % Al₂ O₃) ceramic composition.

FIG. 62 is the electron microscopic photograph (1000 magnification ratio) which explains the structure of crystals of the (0.94MgTiO₃ ·0.06CaTiO₃ +12 wt % Al₂ O₃) ceramic composition.

FIG. 63 is a graph showing the result of X-ray diffraction of a (0.94MgTiO₃ ·0.06CaTiO₃ +3, 6, 9 or 12 wt % Al₂ O₃) ceramic composition.

FIG. 64 is a graph showing a relation between the amount of Al₂ O₃ and Qu in a (0.94MgTiO₃ ·0.06CaTiO₃ +3-12 wt % Co₂ O₃) ceramic composition produced by sintering at each of sintering temperatures.

FIG. 65 is a graph showing a relation between the amount of 3-12 wt % Co₂ O₃ and ε_(r) in the ceramic composition shown in FIG. 64.

FIG. 66 is a graph showing a relation between the amount of 3-12 wt % Co₂ O₃ and τf in the ceramic composition shown in FIG. 64.

FIG. 67 is a graph showing a relation between the amount of 3-12 wt % Co₂ O₃ and the sintering density in the ceramic composition shown in FIG. 64.

FIG. 68 is a graph showing a relation between the sintering temperature and Qu in the (0.94MgTiO₃ ·0.06CaTiO₃ +3-12 wt % Co₂ O₃) ceramic composition.

FIG. 69 is a graph showing a relation between the sintering temperature and ε_(r) in the ceramic composition shown in FIG. 68.

FIG. 70 is a graph showing a relation between the sintering temperature and τf in the ceramic composition shown in FIG. 68.

FIG. 71 is a graph showing a relation between the sintering temperature and the sintering density in the ceramic composition shown in FIG. 68.

FIG. 72 is a graph showing a relation between the sintering temperature and the average grain size in the ceramic composition shown in FIG. 68.

FIG. 73 is a graph showing the result of X-ray diffraction of a (0.94MgTiO₃ ·0.06CaTiO₃ +3, 6 or 12 wt % Co₂ O₃) ceramic composition.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Now, the present invention will be explained specifically by way of examples.

EXAMPLE 1

MgO powder (99.4% purity), CaCO₃ powder for CaO (99% purity), TiO₂ powder (99.98% purity) and ZnO powder (99.5% purity) as the starting material were weighted each by a predetermined amount (about 600 g in total) and mixed so as to provide a composition in which each of x and y varies in the formula xMgTiO₃ ·(1-x)CaTiO₃ +y wt % ZnO (in which y represents parts by weight of ZnO based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃) as shown in Table 1 and FIGS. 1-4. Then, after dry mixing in a mixer (20 to 30 min.) and primary pulverization, they were calcined in an atmospheric air at a temperature of 1100° C. for 2 hours. Subsequently, an appropriate amount of an organic binder (29 g) and water (300-400 g) was added to the calcined powder, which was pulverized together with alumina balls of 20 mmΦ at 90 rpm for 23 hours. Then, the pulverizates were pelletized in vacuum freeze drying (about 0.4 Torr, at 40°-50° C. for about 20 hours), and the thus pelletized raw material was molded into a cylindrical shape of 19 mm Φ×11 mmt (thickness) under a pressing pressure of 1,000 kg/cm².

Subsequently, the molding product was degreased in an atmospheric air at 500° C. for 3 hours and then sintered at each of temperatures with a range of 1300° to 1425° C.

                                      TABLE 1                                      __________________________________________________________________________     [xMgTiO.sub.3.(1 - x)CaTiO.sub.3 + 0˜9 wt % ZnO] ceramic                 composition                                                                                               Rel.                                                        Amount                                                                              Calcining                                                                           Sinter.  dielect.                                                                           τ f                                                                             Sint.                                              of ZnO                                                                              temp.                                                                               temp.                                                                              Qu   const.                                                                             (ppm/                                                                               density                                    No.                                                                               x    (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                        °C.)                                                                         (g/cm.sup.3)                               __________________________________________________________________________     1  0.950                                                                               0    1100 1350                                                                               3540 19.00                                                                              -21.1                                                                               --                                         2  0.950                                                                               3    1100 1350                                                                               4030 20.48                                                                              -10.4                                                                               3.863                                      3  0.950                                                                               6    1100 1350                                                                               4090 20.39                                                                              -14.1                                                                               3.911                                      4  0.950                                                                               9    1100 1350                                                                               --   --  --   --                                         5  0.9475                                                                              0    1100 1350                                                                               2880 16.80                                                                              -16.9                                                                               3.386                                      6  0.9475                                                                              3    1100 1350                                                                               4270 20.05                                                                              -5.07                                                                               3.792                                      7  0.9475                                                                              6    1100 1350                                                                               4300 20.13                                                                              -9.71                                                                               3.847                                      8  0.9475                                                                              9    1100 1350                                                                               4360 20.05                                                                              -14.7                                                                               3.895                                      9  0.943                                                                               0    1100 1350                                                                               3030 17.16                                                                              -11.4                                                                               3.394                                      10 0.943                                                                               3    1100 1350                                                                               4370 19.49                                                                              -7.26                                                                               3.710                                      11 0.943                                                                               6    1100 1350                                                                               4140 20.38                                                                              -5.01                                                                               3.849                                      12 0.943                                                                               9    1100 1350                                                                               4210 20.47                                                                              -8.50                                                                               3.906                                      13 0.940                                                                               0    1100 1350                                                                               3820 18.27                                                                              0.19 3.480                                      14 0.940                                                                               3    1100 1350                                                                               3720 21.52                                                                              19.0 3.834                                      15 0.940                                                                               6    1100 1350                                                                               4000 20.94                                                                              0.50 3.888                                      16 0.940                                                                               9    1100 1350                                                                               3680 21.56                                                                              15.3 3.944                                      17 0.935                                                                               0    1100 1350                                                                               3890 18.39                                                                              7.85 3.467                                      18 0.935                                                                               3    1100 1350                                                                               3530 21.39                                                                              21.9 3.798                                      19 0.935                                                                               6    1100 1350                                                                               3900 21.25                                                                              5.32 3.893                                      20 0.935                                                                               9    1100 1350                                                                               3640 21.83                                                                              17.2 3.954                                      21 0.930                                                                               0    1100 1350                                                                               3820 19.54                                                                              15.1 3.577                                      22 0.930                                                                               3    1100 1350                                                                               3610 21.02                                                                              17.2 3.789                                      23 0.930                                                                               6    1100 1350                                                                               3690 21.64                                                                              16.6 3.896                                      24 0.930                                                                               9    1100 1350                                                                               3780 21.55                                                                              8.86 3.942                                      25 0.925                                                                               0    1100 1350                                                                               3110 18.82                                                                              17.3 3.467                                      26 0.925                                                                               3    1100 1350                                                                               3600 21.13                                                                              21.6 3.758                                      27 0.925                                                                               6    1100 1350                                                                               3670 21.92                                                                              21.1 3.897                                      28 0.925                                                                               9    1100 1350                                                                               3660 21.89                                                                              16.6 3.948                                      __________________________________________________________________________

shown in each of the figures of 4 hours and, finally, both end faces were polished to form cylindrical members each of about 16 mmΦ×8 mmt (thickness) as dielectric specimens.

Then, measurement was conducted for each of the specimens, regarding ε_(r) (relative dielectric constant), Qu and τf by a parallel plate dielectric cylindrical resonator method (TE₀₁₁ MODE) or the like and, further, sintering density by an Archimedes method. τf was measured in a temperature region of 20° C. to 80° C. and calculated as τf=((f(80° C.)-f(20° C.))/(f(20° C.)×ΔT)·ΔT:80° C.-20° C.=60° C. The resonance frequency is 6 GHz. The results are shown in FIGS. 1-11. As an example, results of X-ray diffraction is shown for a case of 0.95MgTiO₃ ·0.05CaTiO₃ in FIG. 12 (containing 6% by weight of ZnO based on 0.95 MgTiO₃ ·0.05CaTiO₃, sintered at 1300° C. for 4 hours) and in FIG. 13 (not containing ZnO, sintered at 1360° C. for 4 hours).

As can be seen from the results, the value Qu tends to decrease if x in xMgTiO₃ ·(1-x)CaTiO₃ is small, whereas τf and ε_(r) tend to increase toward the positive side. The sintering density tends to increase as the sintering temperature is higher, whereas it becomes flat relative to the sintering temperature as the addition amount of ZnO is increased.

At a sintering temperature of 1350° to 1425° C., a preferred range for x is from 0.925 to 0.950, since practical characteristic ranges are shown for τf as +23 to -17 ppm/°C., for ε_(r) as 19 to 22 and for Qu as 3330 to 4390. Particularly, if x=0.940 and the addition amount of ZnO is 6% by weight, at a sintering temperature, for example, of 1350° C. and 1375° C., a particularly excellent balance of characteristics is shown as shown in FIG. 1 to FIG. 6, in which τf is from -1 to +1 ppm/°C., ε_(r) is about 2.1 and Qu is about 4000. Further, with regard to τf, since the variation coefficient relative to the sintering temperature is low, a small value around 0 can be adjusted easily. On the other hand, it is not preferred that CaTiO₃ is not contained since the value Qu is large but ε_(r) is small and τf remarkably decreases toward the negative side as -25 to -44 ppm/° C.

Further, the analysis method based on the absence or presence of X-ray diffraction peak in FIG. 12, shows that the structure of products according to the present invention contains MgTiO₃ (◯), partially containing ZnTiO₃) and CaTiO₃ () and, as other peaks, Mg₂ TiO₄ (Δ partially containing ZnTiO₄) and not containing MgO, CaO and TiO₂. FIG. 13 shows a case not containing ZnO, which shows that the structure comprises MgTiO₃ (◯) and CaTiO₃ (), also shows that MgO, CaO, TiO₂ are not contained.

Further, although not illustrated, results of electron microscopic photograph show that the grain size increases along with elevation of the sintering temperature (1300° C.: 3.1 μm, 1350° C.: 7.2 μm, 1400° C.: 12.8 μm, each measured by Intercept method), pores decrease and densification is completed at 1400° C. The rapture cross section showed grain boundary destruction at 1300° C. and intergrain destruction above 1350° C.

EXAMPLE 2

Using Ta₂ O₅ powder (99.9% purity) instead of the ZnO powder used in Example 1, a predetermined amount of the starting material (about 500 g in total) was weighted and mixed so as to provide a composition in which x and y vary in the formula: x MgTiO₃ ·(1-x)CaTiO₃ +y wt % Ta₂ O₅ in which y means % be weight of Ta₂ O₅ based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃) as shown in Tables 2 and 3 and FIGS. 14 and 17. Subsequently, molding products of the same shape were produced, sintered in the same manner, and then polished to prepare dielectric specimens of the same shape as in Example 1. Further, characteristics were measured by the same method and the results are shown in Tables 2-3 and FIGS. 14-23. Further, as an example, results of X-ray diffraction of 0.93MgTiO₃ ·0.07CaTiO₃ 3 wt % in a case of Ta₂ O₅ are shown in FIG. 24 (sintered at 1300° C. for 4 hours) and in FIG. 25 (sintered at 1350° C. for 4 hours).

From the foregoing results, the value Qu tends to decrease if x is small in x MgTiO₃ ·(1-x)CaTiO₃ but τf and ε_(r) tend to increase toward the positive side. Further, the sintering density tends to increase along with elevation of

                                      TABLE 2                                      __________________________________________________________________________     [xMgTiO.sub.3.(1 - x)CaTiO.sub.3 + 3 wt % Ta.sub.2 O.sub.5 ] ceramic           composition                                                                                               Rel.                                                        Amount                                                                              Calcining                                                                           Sinter.  dielect.                                                                           τ f                                                                             Sint.                                              of Ta.sub.2 O.sub.5                                                                 temp.                                                                               temp.                                                                              Qu   const.                                                                             (ppm/                                                                               density                                    No.                                                                               x    (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                        °C.)                                                                         (g/cm.sup.3)                               __________________________________________________________________________     1  0.940                                                                               3    1100 1400                                                                               4350 20.68                                                                              -12.48                                                                              3.870                                      2  0.9375                                                                              3    1100 1400                                                                               4310 20.82                                                                              -11.0                                                                               3.872                                      3  0.935                                                                               3    1100 1400                                                                               4260 20.97                                                                              -8.50                                                                               3.875                                      4  0.930                                                                               3    1100 1400                                                                               4140 21.28                                                                              -1.47                                                                               3.868                                      5  0.927                                                                               3    1100 1400                                                                               3940 21.50                                                                              1.02 3.875                                      6  0.923                                                                               3    1100 1400                                                                               3850 21.72                                                                              5.10 3.875                                      7  0.940                                                                               3    1100 1375                                                                               4380 20.76                                                                              -11.4                                                                               3.875                                      8  0.9375                                                                              3    1100 1375                                                                               4330 20.88                                                                              -9.40                                                                               3.878                                      9  0.935                                                                               3    1100 1375                                                                               4260 21.07                                                                              -6.58                                                                               3.881                                      10 0.930                                                                               3    1100 1375                                                                               4130 21.39                                                                              0.09 3.876                                      11 0.927                                                                               3    1100 1375                                                                               3890 21.60                                                                              1.70 3.884                                      12 0.923                                                                               3    1100 1375                                                                               3850 21.81                                                                              6.20 3.882                                      13 0.940                                                                               3    1100 1350                                                                               4230 20.77                                                                              -11.4                                                                               3.874                                      14 0.9375                                                                              3    1100 1350                                                                               4190 20.90                                                                              -9.12                                                                               3.874                                      15 0.935                                                                               3    1100 1350                                                                               4180 21.08                                                                              -6.40                                                                               3.881                                      16 0.930                                                                               3    1100 1350                                                                               4030 21.28                                                                              0.65 3.874                                      17 0.927                                                                               3    1100 1350                                                                               3920 21.64                                                                              2.26 3.884                                      18 0.923                                                                               3    1100 1350                                                                               3900 21.87                                                                              6.87 3.882                                      19 0.940                                                                               3    1100 1325                                                                               4230 20.49                                                                              -11.3                                                                               3.835                                      20 0.9375                                                                              3    1100 1325                                                                               4220 20.62                                                                              -8.94                                                                               3.835                                      21 0.935                                                                               3    1100 1325                                                                               4190 20.90                                                                              -5.78                                                                               3.850                                      22 0.930                                                                               3    1100 1325                                                                               4070 21.15                                                                              -0.11                                                                               3.834                                      23 0.927                                                                               3    1100 1325                                                                               3980 21.46                                                                              3.09 3.855                                      24 0.923                                                                               3    1100 1325                                                                               3890 21.61                                                                              7.16 3.844                                      25 0.940                                                                               3    1100 1300                                                                               4130 19.06                                                                              -11.4                                                                               3.640                                      26 0.9375                                                                              3    1100 1300                                                                               4150 19.26                                                                              -9.73                                                                               3.650                                      27 0.935                                                                               3    1100 1300                                                                               4180 19.71                                                                              -6.75                                                                               3.687                                      28 0.930                                                                               3    1100 1300                                                                               4120 20.04                                                                              -0.53                                                                               3.686                                      29 0.927                                                                               3    1100 1300                                                                               4070 20.70                                                                              1.82 3.753                                      30 0.923                                                                               3    1100 1300                                                                               3980 20.59                                                                              6.8  3.706                                      __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________     [xMgTiO.sub.3.(1 - x)CaTiO.sub.3 + 2˜4 wt % Ta.sub.2 O.sub.5 ]           ceramic                                                                        composition                                                                                               Rel.                                                        Amount                                                                              Calcining                                                                           Sinter.  dielect.                                                                           τ f                                                                             Sint.                                              of Ta.sub.2 O.sub.5                                                                 temp.                                                                               temp.                                                                              Qu   const.                                                                             (ppm/                                                                               density                                    No.                                                                               x    (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                        °C.)                                                                         (g/cm.sup.3)                               __________________________________________________________________________     1  0.923                                                                               3    1100 1425                                                                               3840 21.59                                                                              3.92 3.863                                      2  0.927                                                                               3    1100 1425                                                                               3900 21.34                                                                              0.   3.862                                      3  0.930                                                                               2    1100 1425                                                                               4060 21.26                                                                              0.31 3.848                                      4  0.930                                                                               4    1100 1425                                                                               4000 21.05                                                                              -6.27                                                                               3.872                                      5  0.930                                                                               2    1100 1400                                                                               4000 21.37                                                                              0.37 3.861                                      6  0.930                                                                               3    1100 1400                                                                               4140 21.28                                                                              -1.47                                                                               3.868                                      7  0.930                                                                               4    1100 1400                                                                               4000 21.25                                                                              -5.08                                                                               3.889                                      8  0.930                                                                               2    1100 1375                                                                               4000 21.44                                                                              0.81 3.863                                      9  0.930                                                                               3    1100 1375                                                                               4130 21.39                                                                              0.09 3.876                                      10 0.930                                                                               4    1100 1375                                                                               3960 21.31                                                                              -3.52                                                                               3.895                                      11 0.930                                                                               2    1100 1350                                                                               4050 21.47                                                                              1.10 3.865                                      12 0.930                                                                               3    1100 1350                                                                               4030 21.28                                                                              0.65 3.874                                      13 0.930                                                                               4    1100 1350                                                                               3980 21.36                                                                              -2.33                                                                               3.894                                      14 0.930                                                                               2    1100 1325                                                                               4100 21.23                                                                              0.42 3.829                                      15 0.930                                                                               3    1100 1325                                                                               4070 21.15                                                                              -0.11                                                                               3.834                                      16 0.930                                                                               4    1100 1325                                                                               4020 21.10                                                                              -0.76                                                                               3.848                                      17 0.930                                                                               2    1100 1300                                                                               4120 20.27                                                                              0.68 3.698                                      18 0.930                                                                               3    1100 1300                                                                               4120 20.04                                                                              -0.53                                                                               3.686                                      19 0.930                                                                               4    1100 1300                                                                               4020 19.90                                                                              -0.53                                                                               3.686                                      __________________________________________________________________________

the sintering temperature but it becomes flat relative to the sintering temperature as the addition amount of Ta₂ O₅ increases.

At a sintering temperature from 1300° C., a preferred range of x is from 0.923 to 0.940, since practical characteristic ranges are shown for τf as -13 to +8 ppm/° C., for ε_(r) as 19 to 22 and for Qu as 3850 to 4380. Particularly, if x is 0.930 and the addition amount of Ta₂ O₅ is 3% by weight, at a sintering temperature, for example, of 1325° C. to 1375° C., τf is from -0.1 to +0.65 ppm/° C., ε_(r) is from 21.1 to 21.4 and Qu is from 4030 to 4230, as shown in FIG. 14 to FIG. 19 and Tables 2 and 3, showing particularly excellent balance of the characteristics and the scattering thereof is extremely small. On the other hand, it is not preferred that CaTiO₃ is not contained, since the Qu value is large, ε_(r) is small and, in addition, τf extremely decreases toward the negative side as -25 to -44 ppm/° C.

Further, the analysis method based on the absence or presence of X-ray diffraction peaks shown in FIGS. 24 and 25 shows that the structure of products according to the present invention contains MgTiO₃ (◯) and CaTiO₃ () and MgTi205 (∇) as other peaks and that MgO, CaO and TiO2 are not contained.

Further, although not illustrated, results of electron microscopic photograph show that the grain size increases along with the elevation of the sintering temperature (1300° C.:2.5 μm, 1350° C.:3.7 μm, 1400° C.:6.5 μm, each measured by Intercept method), pores decrease and densification is completed at 1350° C. The rapture cross-section shows grain boundary destruction at 1300° C. and intergrain destruction above 1350° C. Further, the surface tissue was classified into two kinds of grains, namely, huge grains (usual grains, 10-50 μm of grain size) and fine square grains (less than 1-10 μm). As a result of EDS (Energy Dispersive Spectrum) analysis, Mg, Ca, Ti and Si were detected from the usual grains while Mg, Ca, Ti and Ta were detected from the square grains. It is considered that the square grains are in the form of Ta compounds. Further, it is considered that the Si ingredient was mixed from the starting material.

EXAMPLE 3

Using Nb₂ O₅ powder (100% purity) instead of the ZnO powder used in Example 1, a predetermined amount of the starting material (about 500 g in total) was weighted and mixed so as to provide a composition in which x and y vary in the formula: xMgTiO₃ ·(1-x)CaTiO₃ +y wt % Nb₂ O₅ in which y means % by weight of Nb₂ O₅ based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃ as shown in Tables 4-6 and FIGS. 26-36.

Table 4 shows the change of the addition amount of MgTiO₃ and Tables 5 and 6 show the change of the addition amount of Nb₂ O₅. Subsequently, molding products of the same shape were produced, sintered in the same manner, and then polished to prepare dielectric specimens of the same shape as in Example 1 (Nos. 1-24 in Table 4 and Nos. 1-36 in Tables 5 and 6). Further, characteristics were measured by the same method and the results are shown in Tables 4-6 and FIGS. 26-36. Further, as an example, results of X-ray diffraction of 0.93MgTiO₃ ·0.07CaTiO₃ are shown in FIG. 37 (containing 2%, 4% or 6% by weight of Nb₂ O₅ to 0.93MgTiO₃ ·0.07CaTiO₃ sintered at 1350° C. for 4 hours).

From the foregoing results, the value Qu tends to decrease if x is small in xMgTiO₃ ·(1-x)CaTiO₃ but τf and ε_(r) tend to increase toward the positive side. Further, the sintering density tends to increase along with elevation of the sintering temperature but it shows no substantial change to the change of the sintering temperature as the addition amount of Nb₂ O₅ increases.

Further, although Qu and ε_(r) do not change so much by the addition of Nb₂ O₅, τf tends to decrease. Accordingly, addition of Nb₂ O₅ is suitable to the control of τf without reducing the performance of Qu and ε_(r). Further, if Nb₂ O₅ is not added, characteristics can not be measured when the sintering temperature is low (1275°-1325° C.) (Table 6). Even upon sintering at 1350°-1400° C., although characteristics can be measured τf is remarkably large (Table 5 and FIG. 31; 19.7 (No. 1) and 17.5 (No. 7), 15.1 ppm/°C. (No. 13)). The sintering density is also low upon

                                      TABLE 4                                      __________________________________________________________________________     [xMgTiO.sub.3.(1 - x)CaTiO.sub.3 + 2 wt % Nb.sub.2 O.sub.5 ] ceramic           composition                                                                                               Rel.                                                        Amount                                                                              Calcining                                                                           Sinter.  dielect.                                                                           τ f                                                                             Sint.                                              of Nb.sub.2 O.sub.5                                                                 temp.                                                                               temp.                                                                              Qu   const.                                                                             (ppm/                                                                               density                                    No.                                                                               x    (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                        °C.)                                                                         (g/cm.sup.3)                               __________________________________________________________________________     1  0.940                                                                               2    1100 1400                                                                               4380 20.77                                                                              -11.0                                                                               3.816                                      2  0.935                                                                               2    1100 1400                                                                               4250 21.08                                                                              -6.50                                                                               3.821                                      3  0.930                                                                               2    1100 1400                                                                               4100 21.36                                                                              -0.76                                                                               3.821                                      4  0.925                                                                               2    1100 1400                                                                               3930 21.71                                                                              4.95 3.824                                      5  0.940                                                                               2    1100 1375                                                                               4220 20.87                                                                              -10.8                                                                               3.828                                      6  0.935                                                                               2    1100 1375                                                                               4130 21.19                                                                              -6.26                                                                               3.832                                      7  0.930                                                                               2    1100 1375                                                                               3980 21.48                                                                              -0.16                                                                               3.830                                      8  0.925                                                                               2    1100 1375                                                                               3900 21.82                                                                              5.71 3.831                                      9  0.940                                                                               2    1100 1350                                                                               4230 20.92                                                                              -10.1                                                                               3.828                                      10 0.935                                                                               2    1100 1350                                                                               4150 21.23                                                                              -5.55                                                                               3.834                                      11 0.930                                                                               2    1100 1350                                                                               4030 21.51                                                                              0.51 3.831                                      12 0.925                                                                               2    1100 1350                                                                               3920 21.86                                                                              8.01 3.834                                      13 0.940                                                                               2    1100 1325                                                                               4260 20.77                                                                              -11.0                                                                               3.805                                      14 0.935                                                                               2    1100 1325                                                                               4160 21.16                                                                              -5.58                                                                               3.821                                      15 0.930                                                                               2    1100 1325                                                                               4050 21.44                                                                              0.52 3.817                                      16 0.925                                                                               2    1100 1325                                                                               3940 21.73                                                                              6.40 3.815                                      17 0.940                                                                               2    1100 1300                                                                               4540 20.07                                                                              -11.72                                                                              3.716                                      18 0.935                                                                               2    1100 1300                                                                               4320 20.73                                                                              -6.21                                                                               3.757                                      19 0.930                                                                               2    1100 1300                                                                               4250 20.95                                                                              -0.92                                                                               3.755                                      20 0.925                                                                               2    1100 1300                                                                               4160 21.15                                                                              7.49 3.739                                      21 0.940                                                                               2    1100 1275                                                                               4010 17.87                                                                              -13.0                                                                               3.444                                      22 0.935                                                                               2    1100 1275                                                                               4470 18.97                                                                              -8.20                                                                               3.543                                      23 0.930                                                                               2    1100 1275                                                                               4320 19.05                                                                              -3.69                                                                               3.532                                      24 0.925                                                                               2    1100 1275                                                                               4040 18.99                                                                              1.16 3.487                                      __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________     [0.93 MgTiO.sub.3.0.07 CaTiO.sub.3 + 0˜6 wt % Nb.sub.2 O.sub.5 ]         ceramic                                                                        composition                                                                       Amount                                                                              Calcining                                                                           Sinter.  Rel. dielect.                                                                         τ f                                                                             Sint.                                           of Nb.sub.2 O.sub.5                                                                 temp.                                                                               temp.                                                                              Qu   const. (ppm/                                                                               density                                      No.                                                                               (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                           °C.)                                                                         (g/cm.sup.3)                                 __________________________________________________________________________     1  0    1100 1400                                                                               3490 21.78  19.7 3.834                                        2  1    1100 1400                                                                               2740 21.10  -8.19                                                                               3.820                                        3  2    1100 1400                                                                               4100 21.36  -0.76                                                                               3.821                                        4  3    1100 1400                                                                               4140 21.34  -3.64                                                                               3.817                                        5  4    1100 1400                                                                               4170 21.33  -7.27                                                                               3.819                                        6  6    1100 1400                                                                               4130 21.26  -11.6                                                                               3.812                                        7  0    1100 1375                                                                               3650 21.22  17.5 3.769                                        8  1    1100 1375                                                                               2260 21.16  -7.63                                                                               3.823                                        9  2    1100 1375                                                                               3980 21.48  -0.16                                                                               3.830                                        10 3    1100 1375                                                                               4120 21.55  -2.47                                                                               3.829                                        11 4    1100 1375                                                                               4160 21.55  -6.14                                                                               3.833                                        12 6    1100 1375                                                                               4110 21.52  -9.93                                                                               3.830                                        13 0    1100 1350                                                                               3820 19.54  15.1 3.577                                        14 1    1100 1350                                                                               4190 21.49  1.71 3.829                                        15 2    1100 1350                                                                               4030 21.51  0.51 3.831                                        16 3    1100 1350                                                                               4120 21.55  -1.57                                                                               3.833                                        17 4    1100 1350                                                                               4130 21.59  -4.63                                                                               3.837                                        18 6    1100 1350                                                                               4110 21.56  -9.00                                                                               3.837                                        __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________     [0.93 MgTiO.sub.3.0.07 CaTiO.sub.3 + 0˜6 wt % Nb.sub.2 O.sub.5 ]         ceramic                                                                        composition                                                                       Amount                                                                              Calcining                                                                           Sinter.  Rel. dielect.                                                                         τ f                                                                             Sint.                                           of Nb.sub.2 O.sub.5                                                                 temp.                                                                               temp.                                                                              Qu   const. (ppm/                                                                               density                                      No.                                                                               (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                           °C.)                                                                         (g/cm.sup.3)                                 __________________________________________________________________________     19 0    1100 1325                                                                               Unmeasurable     3.131                                        20 1    1100 1325                                                                               4250 21.25  0.53 3.799                                        21 2    1100 1325                                                                               4050 21.44  0.52 3.817                                        22 3    1100 1325                                                                               4140 21.49  -2.04                                                                               3.816                                        23 4    1100 1325                                                                               4080 21.57  -3.86                                                                               3.831                                        24 6    1100 1325                                                                               4040 21.58  -8.16                                                                               3.829                                        25 0    1100 1300                                                                               Unmeasurable                                                  26 1    1100 1300                                                                               4310 20.53  1.59 3.704                                        27 2    1100 1300                                                                               4250 20.95  -0.92                                                                               3.755                                        28 3    1100 1300                                                                               4200 21.03  -2.49                                                                               3.762                                        29 4    1100 1300                                                                               4070 21.34  -3.18                                                                               3.792                                        30 6    1100 1300                                                                               4070 21.39  - 8.24                                                                              3.801                                        31 0    1100 1275                                                                               Unmeasurable                                                  32 1    1100 1275                                                                               Unmeasurable     3.390                                        33 2    1100 1275                                                                               4320 19.05  -3.69                                                                               3.532                                        34 3    1100 1275                                                                               3740 18.92  -5.80                                                                               3.508                                        35 4    1100 1275                                                                               4230 19.97  -4.93                                                                               3.621                                        36 6    1100 1275                                                                               4190 19.90  -9.14                                                                               3.624                                        __________________________________________________________________________

sintering at 1375° C. or 1350° C. (No. 7 and No. 13 in Table 5).

At a sintering temperature from 1300° to 1400° C. and the addition amount of Nb₂ O₅ of 2% by weight, a preferred range of x is from 0.925 to 0.940, since practical characteristic ranges are shown for τf as -11.72 to +8.01 ppm/°C. for ε_(r) as 20.07 to 21.86 and for Qu as 3900 to 4540. Particularly, if x is 0.930 and the addition amount of Nb₂ O₅ is 2% by weight at a sintering temperature, for example, of 1350° C. and 1375° C., τf is -0.16 to +0.51 ppm/°C, ε_(r) is 21.48 to 21.51 and Qu is 3980 to 4030, showing particularly excellent performance balance with scarce scattering thereof. Further, regarding τf, a small value around 0 ppm/°C. can be controlled easily since the variation coefficient to the sintering temperature is low. On the other hand, it is not preferred that CaTiO₃ is not contained, since the Qu value is large, but ε_(r) is small and, in addition, τf extremely decreases toward the negative side as -25 to -44 ppm/°C.

Further, the analysis method based on the absence or presence of X-ray diffraction peaks in FIG. 37 shows that the structure of products according to the present invention contains MgTiO₃ (◯)) and CaTiO₃ () and MgTi₂ O₅ (Δ) as other peaks and that MgO, CaO and TiO2 are not contained. Further, peaks for Nb₂ O₅ compounds were not detected. However, although a diffraction pattern is substantially the same for the addition amount of Nb₂ O₅, peaks for MgTiO₃ and MgTi₂ O₅ shifted slightly to the lower angle side of 2θ--along with increase of the addition amount from 2 to 6% by weight (FIG. 37). Accordingly, it is considered that Nb⁵⁺ ions are solid solubilized in MgTiO₃ and MgTi₂ O₅.

Further, although not illustrated, results of electron microscopic photograph show that the grain size increases along with the elevation of the sintering temperature (1275° C.:2.6 μm, 1300° C.:3.1 μm, 1350° C.:4.9 μm and 1400° C.:6.1 μm, each measured by an Intercept method), and pores decrease, showing that densification is completed at 1350° C. The rapture cross-section shows inter-grain destruction for each of the cases.

EXAMPLE 4

Using MnO₂ powder (96% purity) instead of the ZnO powder used in Example 1, a predetermined amount of the starting material (about 500 g in total) was weighted and mixed so as to provide a composition in which x and y vary in the formula: xMgTiO₃ ·(1-x)CaTiO₃ +y wt % MnO₂ in which y means % by weight of MnO₂ based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃ as shown in Tables 7-10 and FIGS. 38 and 42. Table 7 shows the change of the addition amount (constitutional amount of CaTiO₃ and Tables 8-10 show the change of the addition amount of MnO₂. Subsequently, molding products of the same shape were produced, sintered in the same manner, and then polished to prepare dielectric

                                      TABLE 7                                      __________________________________________________________________________     [xMgTiO.sub.3.(1 - x)CaTiO.sub.3 ] ceramic composition (x                      = 0.97˜0.93)                                                                    Calcining                                                                           Sinter.  Rel. dielect.                                                                         τ f                                                                             Sint.                                                temp.                                                                               temp.                                                                              Qu   const. (ppm/                                                                               density                                       No.                                                                               1 - x                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                           °C.)                                                                         (g/cm.sup.3)                                  __________________________________________________________________________     1  0.03                                                                               1100 1425                                                                               4020 18.60  -49.6                                                                               3.765                                         2  0.05                                                                               1100 1425                                                                               2840 19.82  -33.8                                                                               3.803                                         3  0.07                                                                               1100 1425                                                                               2390 21.17  -4.47                                                                               3.819                                         4  0.03                                                                               1100 1400                                                                               3800 18.58  -47.8                                                                               3.758                                         5  0.05                                                                               1100 1400                                                                               2900 19.79  -28.6                                                                               3.803                                         6  0.07                                                                               1100 1400                                                                               3490 21.78  19.72                                                                               3.834                                         7  0.03                                                                               1100 1375                                                                               4820 18.61  -33.3                                                                               3.716                                         8  0.05                                                                               1100 1375                                                                               4190 19.81  -9.63                                                                               3.746                                         9  0.07                                                                               1100 1375                                                                               3650 21.22  17.5 3.769                                         10 0.03                                                                               1100 1350                                                                               4700 17.06  -34.4                                                                               3.529                                         11 0.05                                                                               1100 1350                                                                               4230 18.22  -11.7                                                                               3.543                                         12 0.07                                                                               1100 1350                                                                               3820 19.54  15.1 3.577                                         13 0.03                                                                               1100 1325                                                                               1150 13.56  -42.8                                                                               3.057                                         14 0.05                                                                               1100 1325                                                                               Unmeasurable     3.072                                         15 0.07                                                                               1100 1325                                                                               Unmeasurable     3.131                                         __________________________________________________________________________

                                      TABLE 8                                      __________________________________________________________________________     [0.94 MgTiO.sub.3.0.06 CaTiO.sub.3 + 0˜6 wt % MnO.sub.2 ] ceramic        composition                                                                       Amount                                                                              Calcining                                                                           Sinter.  Rel. dielect.                                                                         τ f                                                                             Sint.                                           of MnO.sub.2                                                                        temp.                                                                               temp.                                                                              Qu   const. (ppm/                                                                               density                                      No.                                                                               (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                           °C.)                                                                         (g/cm.sup.3)                                 __________________________________________________________________________     1  3    1100 1425                                                                               3570 20.86  0.56 3.841                                        2  6    1100 1425                                                                               3090 20.68  -2.38                                                                               3.854                                        3  3    1100 1400                                                                               3640 20.95  1.78 3.847                                        4  6    1100 1400                                                                               3080 20.79  -1.21                                                                               3.861                                        5  3    1100 1375                                                                               3700 20.68  -0.09                                                                               3.815                                        6  6    1100 1375                                                                               3080 20.84  0.20 3.862                                        7  3    1100 1350                                                                               3890 19.04  -2.60                                                                               3.616                                        8  6    1100 1350                                                                               3150 20.45  -1.23                                                                               3.807                                        9  3    1100 1325                                                                                660 17.00  -3.26                                                                               3.384                                        10 6    1100 1325                                                                               3360 18.52  -4.36                                                                               3.578                                        11 3    1100 1300                                                                               Unmeasurable     3.255                                        12 6    1100 1300                                                                               Unmeasurable     3.418                                        13 0    1100 1425                                                                               2480 20.46   -23.0                                                                              3.815                                        14 0    1100 1400                                                                               3360 20.51  -18.0                                                                               3.812                                        15 0    1100 1375                                                                               3940 20.83  4.84 3.778                                        16 0    1100 1350                                                                               3820 18.27  0.19 3.480                                        17 0    1100 1325                                                                                430 16.28  3.72 3.266                                        18 0    1100 1300                                                                               Unmeasurable     3.121                                        __________________________________________________________________________

                                      TABLE 9                                      __________________________________________________________________________     [0.95 MgTiO.sub.3.0.05 CaTiO.sub.3 + 0.1˜0.6 wt % MnO.sub.2 ]            ceramic composition                                                               Amount                                                                              Calcining                                                                           Sinter.  Rel. dielect.                                                                         τ f                                                                             Sint.                                           of MnO.sub.2                                                                        temp.                                                                               temp.                                                                              Qu   const. (ppm/                                                                               density                                      No.                                                                               (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                           °C.)                                                                         (g/cm.sup.3)                                 __________________________________________________________________________     1  0.1  1100 1400                                                                               3790 19.80  -31.4                                                                               3.804                                        2  0.2  1100 1400                                                                               3810 19.83  -31.3                                                                               3.807                                        3  0.3  1100 1400                                                                               3660 19.85  -30.7                                                                               3.814                                        4  0.6  1100 1400                                                                               3850 19.83  -29.6                                                                               3.818                                        5  0.1  1100 1375                                                                               3970 20.21  -11.8                                                                               3.805                                        6  0.2  1100 1375                                                                               4030 20.21  -10.7                                                                               3.804                                        7  0.3  1100 1375                                                                               4100 20.27  -9.31                                                                               3.807                                        8  0.6  1100 1375                                                                               4060 20.25  -9.87                                                                               3.810                                        9  0.1  1100 1350                                                                               4220 19.50  -10.4                                                                               3.713                                        10 0.2  1100 1350                                                                               4270 19.30  -10.7                                                                               3.693                                        11 0.3  1100 1350                                                                               4280 19.20  -11.6                                                                               3.683                                        12 0.6  1100 1350                                                                               4250 19.34  -11.1                                                                               3.703                                        13 0.1  1100 1325                                                                               3950 17.42  -13.4                                                                               3.449                                        14 0.2  1100 1325                                                                               3970 17.41  -12.7                                                                               3.462                                        15 0.3  1100 1325                                                                               3550 17.05  -14.2                                                                               3.422                                        16 0.6  1100 1325                                                                               3650 17.10  -14.1                                                                               3.426                                        17 0.1  1100 1300                                                                               1090 15.43  -26.4                                                                               3.230                                        18 0.2  1100 1300                                                                               1010 15.56  -30.2                                                                               3.251                                        19 0.3  1100 1300                                                                               1450 15.41  -21.5                                                                               3.232                                        20 0.6  1100 1300                                                                                950 15.54  -23.7                                                                               3.245                                        __________________________________________________________________________

                                      TABLE 10                                     __________________________________________________________________________     [0.93 MgTiO.sub.3.0.07 CaTiO.sub.3 + 0˜6 wt % MnO.sub.2 ] ceramic        composition                                                                       Amount                                                                              Calcining                                                                           Sinter.  Rel. dielect.                                                                         τ f                                                                             Sint.                                           of MnO.sub.2                                                                        temp.                                                                               temp.                                                                              Qu   const. (ppm/                                                                               density                                      No.                                                                               (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                           °C.)                                                                         (g/cm.sup.3)                                 __________________________________________________________________________     1  3    1100 1425                                                                               3310 21.64  14.3 3.844                                        2  6    1100 1425                                                                               2900 21.38  12.8 3.855                                        3  3    1100 1400                                                                               3330 21.60  15.0 3.851                                        4  6    1100 1400                                                                               2880 21.42  12.3 3.864                                        5  3    1100 1375                                                                               3400 21.46  13.8 3.833                                        6  6    1100 1375                                                                               2890 21.44  11.8 3.865                                        7  3    1100 1350                                                                               3560 20.06  11.8 3.668                                        8  6    1100 1350                                                                               2960 21.00  12.0 3.803                                        9  3    1100 1325                                                                               1390 17.71  6.92 3.416                                        10 6    1100 1325                                                                               3140 18.90  7.07 3.563                                        11 3    1100 1300                                                                               Unmeasurable     3.268                                        12 6    1100 1300                                                                               Unmeasurable     3.395                                        13 0    1100 1425                                                                               2390 21.17  -4.47                                                                               3.819                                        14 0    1100 1400                                                                               3490 21.78  19.7 3.834                                        15 0    1100 1375                                                                               3650 21.22  17.5 3.769                                        16 0    1100 1350                                                                               3820 19.54  15.1 3.577                                        17 0    1100 1325                                                                               Unmeasurable     3.131                                        __________________________________________________________________________

specimens of the same shape as in Example 1 (Nos. 1-18 in Table 8, Nos. 1-20 in Table 9 and Nos. 1-17 in Table 10). Further, characteristics were measured by the same method. The results are shown in Tables 8-10 and FIGS. 38-49. Further, as an example, results of X-ray diffraction of 0.94MgTiO₃ ·0.06CaTiO₃ are shown in FIG. 50 (containing 0%, 3% or 6% by weight of MnO₂ to 0.94MgTiO₃ ·0.06 CaTiO₃ sintered at 1300° C. for 4 hours).

From the foregoing results, the value Qu tends to decrease if (1-x) is large in xMgTiO₃ ·(1-x)CaTiO₃, whereas τf and ε_(r) tend to increase toward the positive side. Further, the sintering density tends to increase along with elevation of the sintering temperature but it shows no substantial change relative to the change of the sintering temperature as the addition amount of MnO₂ increases.

Further, although ε_(r) shows no substantial change, Qu and τf tend to decrease due to the addition of MnO₂. Accordingly, addition of MnO₂ is suitable to the control of τf with no reduction of the performance of ε_(r). Further, as shown in Table 8, in a case if MnO₂ is not added, the sintering density is small if the sintering temperature is low (1325° to 1350° C.) and a temperature higher than 1375° C. is necessary for ensuring a sufficient sinterability. On the other hand, in a case of adding MnO₂ (3 to 6% by weight), a sufficient sinterability is shown even at a sintering temperature of 1350° C.

At a sintering temperature from 1350° to 1425° C. and with the addition amount of MnO₂ of 3% by weight, a preferred range of (1-x) is from 0.06 to 0.07, since practical characteristic ranges are shown for τf as -2.60 to +15.0 ppm/°C., for ε_(r) as 19.04 to 21.64 and for Qu as 3310 to 3890. Particularly, if (1-x) is 0.06 and the addition amount of MnO₂ is 3% by weight, at a sintering temperature, for example, of 1375° C., τf is -0.09 ppm/°C., ε_(r) is 20.7 and Qu is 3700, showing particularly excellent balance of performance and the scattering thereof is extremely small. Further, regarding τf, since the variation coefficient to the sintering temperature is low, a small value around zero ppm/°C. can be controlled easily. On the other hand, it is not preferred that CaTiO₃ is not contained, since the Qu value is large, but ε_(r) is small and, in addition, τf extremely decreases toward the negative side as -25 to -44 ppm/°C.

Further, the analysis method based on the absence or presence of X-ray diffraction peaks shown in FIG. 50 shows that the structure of products according to the present invention contains MgTiO₃ (◯) and CaTiO₃ () and Mg₆ MnO₆ (Δ) and Mn₃ O₄ (∇) as other peaks and that MgO, CaO and TiO2 are not contained. Namely, the relative peak intensity of MgTiO₃ is reduced along with the increase of the addition amount of MnO₂, while Mg₆ MnO₈, Mn₃ O₄, etc., are increased. It is considered that Qu decreases due to the decrease in the amount of MgTiO₃.

Further, although not illustrated, results of electron microscopic photograph show that the grain size increases along with the elevation of the sintering temperature (1300° C.:2.7 μm, 1350° C.:8.7 μm, 1400° C.:9.2 μm, each measured by an Intercept method). The rapture cross-section shows inter-grain destruction in each of the cases. As a result of EDS analysis, only Mg, Ca, Ti and Mn were detected.

EXAMPLE 5

Using Al₂ O₃ powder (99.9% purity) instead of the ZnO powder used in Example 1, a predetermined amount of the starting material (about 500 g in total) was weighted and mixed so as to provide a composition in which x and y vary in the formula: xMgTiO₃ ·(1-x)CaTiO₃ +y wt % Al₂ O₃ in which y means % by weight of Al₂ O₃ based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃ in Tables 7 and 11 and FIGS. 51-58. Table 7 shows the change of the addition amount (constitutional amount) of CaTiO₃ (1-x) and Tables 11 shows the change of the addition amount of Al₂ O₃. Subsequently, molding products of the same shape were produced, sintered in the same manner at a predetermined temperature and then polished to prepare dielectric specimens of the same shape as in Example 1 (Nos. 1-12 in Table 7 and Nos. 1-24 in Table 11). Further, characteristics were measured by the same method. The results are shown in Table 7 and 11 and FIGS.

                                      TABLE 11                                     __________________________________________________________________________     [0.94 MgTiO.sub.3.0.06 CaTiO.sub.3 + 3˜12 wt % Al.sub.2 O.sub.3 ]        ceramic composition                                                               Amount                                                                              Calcining                                                                           Sinter.  Rel. dielect.                                                                         τ f                                                                             Sint.                                           of Al.sub.2 O.sub.3                                                                 temp.                                                                               temp.                                                                              Qu   const. (ppm/                                                                               density                                      No.                                                                               (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                           °C.)                                                                         (g/cm.sup.3)                                 __________________________________________________________________________     1  12   1100 1425                                                                               4040 18.90  -13.2                                                                               3.725                                        2  9    1100 1400                                                                               3940 19.47  -11.3                                                                               3.756                                        3  12   1100 1400                                                                               4000 19.10  -13.2                                                                               3.739                                        4  3    1100 1375                                                                               3550 20.54  -2.21                                                                               3.811                                        5  6    1100 1375                                                                               3530 20.07  -3.85                                                                               3.781                                        6  9    1100 1375                                                                               3700 19.70  -5.50                                                                               3.762                                        7  12   1100 1375                                                                               3860 19.34  -5.77                                                                               3.739                                        8  3    1100 1350                                                                               3560 20.60  -0.70                                                                               3.816                                        9  6    1100 1350                                                                               3390 20.13  -0.74                                                                               3.781                                        10 9    1100 1350                                                                               3640 19.68  -1.53                                                                               3.747                                        11 12   1100 1350                                                                               3750 19.09  -2.06                                                                               3.698                                        12 3    1100 1325                                                                               3530 20.56  0.97 3.802                                        13 6    1100 1325                                                                               3360 20.00  1.91 3.759                                        14 9    1100 1325                                                                               3600 19.29  0    3.696                                        15 12   1100 1325                                                                               3850 18.20  -1.99                                                                               3.593                                        16 3    1100 1300                                                                               3470 20.24  2.25 3.762                                        17 6    1100 1300                                                                               3370 19.50  2.59 3.695                                        18 9    1100 1300                                                                               3730 18.40  0.12 3.568                                        19 12   1100 1300                                                                               3870 16.39  -5.22                                                                               3.376                                        20 3    1100 1275                                                                               3590 19.20  2.37 3.607                                        21 6    1100 1275                                                                               3470 18.05  1.76 3.517                                        22 9    1100 1275                                                                               2640 15.77  -6.50                                                                               3.298                                        23 3    1100 1250                                                                               2870 16.18  -2.39                                                                               3.287                                        24 6    1100 1250                                                                               2810 15.15  -2.87                                                                               3.203                                        __________________________________________________________________________

51-58. The resonance frequency used for the measurement of Qu is 5.7 to 6.3 GHz. Further, FIG. 29 shows a relation between the addition amount of Al₂ O₃ and the average grain size of the sintering product and FIG. 60 shows a relation between the sintering temperature and the average grain size of the sintering product. Further, as an example, FIG. 63 shows results of X-ray diffraction of 0.94MgTiO₃ ·0.06CaTiO₃ ·3.12 wt % Al₂ O₃ (sintered at 1350° C. for 4 hours).

From the foregoing results, the value Qu tends to decrease if (1-x) is large in xMgTiO₃ ·(1-x)CaTiO₃ but τf and ε_(r) tend to increase toward the positive side. Further, the sintering density tends to increase along with elevation of the sintering temperature.

As the addition of Al₂ O₃, increases, Qu tends to increase, and ε_(r), τf and the sintering density tend to decrease. Then, at a sintering temperature of 1275° C., Qu, ε_(r) and the sintering density tend to decrease and their scattering is large, whereas highly stable performances are shown at 1300° to 1375° C. Further, in a case where the addition amount of Al₂ O₃ is 3 to 9% by weight and the sintering temperature is 1300° to 1375° C., well balanced performance and physical property are shown, as Qu is 3360 to 3730, ε_(r) is 18.4 to 20.6, τf is -2.2 to +2.6 ppm/°C. and the sintering density is 3.568 to 3.816 g/cm³ as described above.

In view of the above, appropriate addition of Al₂ O₃ can improve the performance of Qu while maintaining ε_(r) and further it is suitable to the control of τf. Particularly, regarding τf, since the variation coefficient relative to the addition of Al₂ O₃ and the sintering temperature is low, a small value around 0 ppm/°C. can be controlled easily.

Further, as shown in FIG. 60, the grain size of crystal grains increases along with the elevation of the sintering temperature (1300° C.:1.61 μm, 1350° C.:2.19 μm, and 1400° C.:4.46 μm, each measured by an Intercept method), whereas the grain size decreased along with the increase of the addition amount of Al₂ O₃ as shown in FIG. 59 (3 wt %: 3.97, 6 wt %:3.76, 12 wt %:2.19). Further, FIG. 61 is a view explaining the structure of crystals by electron microscopic photograph (1000 magnification ratio) for a composition containing 6 wt % Al₂ O₃ added (sintered at 1350° C. for 4 hours) and FIG. 62 shows a view explaining the structure of crystals by electron microscopic photograph (1000 magnification ratio) for a composition containing 12 wt % Al₂ O₃ added (sintered at 1350° C. for 4 hours). According to the figures, each of them shows substantially uniform grain size distribution. Further, rapture cross-section tissues inter-grain destruction for each of 3-12 wt % Al₂ O₃ addition systems.

Further, the analysis method based on the presence or absence of X-ray diffraction peak in FIG. 63 shows that the structure of products according to the present invention contains MgTiO₃ (◯) and CaTiO₃ () and MgTi₂ O₅ (Δ) as other peaks and that reaction products with Al₂ O₃ are not contained.

EXAMPLE 6

Using Co₂ O₃ powder (99.1% purity) instead of the ZnO powder used in Example 1, a predetermined amount of the starting material (about 500 g in total) was weighted and mixed so as to provide a composition in which x and y vary in the formula: x MgTiO₃ ·(1-x)CaTiO₃ +y wt % Co₂ O₃ in which y means % by weight of Co₂ O₃ based on 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃ as shown in Tables 7 and 12-13 and FIGS. 64-71. Subsequently, molding products of the same shape were produced, sintered in the same manner, and then polished to prepare dielectric specimens of the same shape as in Example 1 (Nos. 1-12 in Table 7, in Nos. 1-24 in Table 12 and Nos. 25 and 26 in Table 13). Further, characteristics were measured by the same method. The results are shown in Tables 7 and 12-13 and FIGS. 64-71. Further, as an example, results of X-ray diffraction of 0.94MgTiO₃ ·0.06CaTiO₃ ·3 wt %, 6 wt % or 12 wt % Co₂ O₃ ceramic composition (sintered at 1300° C. for 4 hours) are shown in FIG. 73.

From the foregoing results, the value Qu tends to decrease, whereas τf and ε_(r) tend to increase toward the

                                      TABLE 12                                     __________________________________________________________________________     [0.94 MgTiO.sub.3.0.06 CaTiO.sub.3 + 3˜12 wt % Co.sub.2 O.sub.3 ]        ceramic composition                                                               Amount                                                                              Calcining                                                                           Sinter.  Rel. dielect.                                                                         τ f                                                                             Sint.                                           of Co.sub.2 O.sub.3                                                                 temp.                                                                               temp.                                                                              Qu   const. (ppm/                                                                               density                                      No.                                                                               (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                           °C.)                                                                         (g/cm.sup.3)                                 __________________________________________________________________________     1  3    1100 1450                                                                               3920 20.77  -0.26                                                                               3.849                                        2  6    1100 1450                                                                               3780 20.58  -0.40                                                                               3.851                                        3  9    1100 1450                                                                               3710 20.37  -2.14                                                                               3.884                                        4  12   1100 1450                                                                               3640 20.17  -0.99                                                                               3.893                                        5  3    1100 1425                                                                               3920 20.91  1.36 3.854                                        6  6    1100 1425                                                                               3840 20.72  -0.74                                                                               3.878                                        7  9    1100 1425                                                                               3750 20.54  -1.79                                                                               3.903                                        8  12   1100 1425                                                                               3680 20.32  -3.29                                                                               3.921                                        9  3    1100 1400                                                                               3900 21.00  1.64 3.864                                        10 6    1100 1400                                                                               3840 20.78  -0.05                                                                               3.889                                        11 9    1100 1400                                                                               3790 20.60  -1.92                                                                               3.914                                        12 12   1100 1400                                                                               3700 20.43  -3.13                                                                               3.935                                        13 3    1100 1375                                                                               4070 20.80  1.11 3.843                                        14 6    1100 1375                                                                               3870 20.82  -0.10                                                                               3.894                                        15 9    1100 1375                                                                               3840 20.68  -1.66                                                                               3.921                                        16 12   1100 1375                                                                               3740 20.49  -2.26                                                                               3.943                                        17 3    1100 1350                                                                               4180 19.36  1.65 3.669                                        18 6    1100 1350                                                                               3970 20.35  -0.03                                                                               3.832                                        19 9    1100 1350                                                                               3860 20.48  -1.12                                                                               3.893                                        20 12   1100 1350                                                                               3760 20.46  -1.87                                                                               3.934                                        21 3    1100 1325                                                                               2400 17.38  -4.95                                                                               3.440                                        22 6    1100 1325                                                                               4160 18.38  -3.02                                                                               3.596                                        23 9    1100 1325                                                                               4020 18.82  -3.42                                                                               3.688                                        24 12   1100 1325                                                                               3860 19.34  -3.02                                                                               3.792                                        __________________________________________________________________________

                                      TABLE 13                                     __________________________________________________________________________     [xMgTiO.sub.3.(1 - x)CaTiO.sub.3 + 6 wt % Co.sub.2 O.sub.3 ] ceramic           composition                                                                                               Rel.                                                        Amount                                                                              Calcining                                                                           Sinter.  dielect.                                                                           τ f                                                                             Sint.                                              of Co.sub.2 O.sub.3                                                                 temp.                                                                               temp.                                                                              Qu   const.                                                                             (ppm/                                                                               density                                    No.                                                                               1 - x                                                                               (wt %)                                                                              (°C.)                                                                        (°C.)                                                                       (6 GHz)                                                                             ε r                                                                        °C.)                                                                         (g/cm.sup.3)                               __________________________________________________________________________     25 0.05 6    1100 1375                                                                               4100 20.10                                                                              -11.2                                                                               3.890                                      14 0.06 6    1100 1375                                                                               3870 20.82                                                                              -0.10                                                                               3.894                                      26 0.07 6    1100 1375                                                                               3650 21.63                                                                              10.8 3.892                                      __________________________________________________________________________

positive side if (1-x) is large in xMgTiO₃ ·(1-x)CaTiO₃. Further, the sintering density tends to increase along with the elevation of the sintering temperature.

Further, although ε_(r) shows no substantial change Qu and τf tend to decrease and the sintering density tends to increase by the addition of Co₂ O₃. Particularly, is (1-x) is 0.06 and the addition amount of Co₂ O₃. Particularly, if (1-x) is 0.06 and the addition amount of Co₂ O₃ is 6% by weight, τf is -0.10 ppm/°C., ε_(r) is 20.82, Qu is 3870 and the sintering density is 3.894 at a sintering temperature, for example, of 1375° C., showing particularly excellent performance balance. Further, at a sintering temperature of 1350° to 1450° C., each of Qu, ε_(r) and τf scarcely scatters (for example, in case of Co₂ O₃ 6 wt %, 3780 to 3970, 20.35 to 20.82, -0.03 to -0.74 ppm/°C., respectively) and products of desired quality can be obtained stably. Further, even if addition amount of Co₂ O₃ changed, each of Qu, ε_(r) and τf scarcely scatters (for instance at a sintering temperature of 1400° C., 3700 to 3900, 20.43 to 21.00, -0.05 to -3.13 ppm/°C., successively). Accordingly, even if the addition amount of Co₂ O₃ and the sintering temperature are changed, products of extremely stable quality can be obtained. Particularly, fine control for τf can be conducted extremely easily.

Further, the analysis method based on the absence or presence of X-ray diffraction peaks in FIG. 73 shows that the structure of products according to the present invention contains MgTiO₃ (◯) and CaTiO₃ () and MgTi204 () as other peaks and that reaction products with Co₂ O₃ are not contained. Further, the relative peak intensity of MgTiO₃ is reduced along with the increase of the addition amount of Co₂ O₃ while the intensity of MgTi₂ O₄ is increased. It is considered that Qu decreases due to the decrease in the amount of MgTiO₃.

Further, results of electron microscopic photograph (not illustrated) show that the grain size increases along with the elevation of the sintering temperature (1350° C.:4.30 μm, 1400° C.:5.32 μm, 1450° C.:7.20 μm, each measured by an Intercept method) as showned in Table 72 . The rapture cross-section tissue shows inter-grain destruction in each of the cases.

The present invention is not restricted to specific embodiments described above but can be modified into various other embodiments depending on the purpose and the application use within the scope of the invention. That is, the calcining conditions such as calcining temperature and sintering conditions such as sintering temperature can be selected variously. Further, also for the starting material for CaO, peroxides, hydroxides and nitrates and so on can also be used in addition to CaCO₃ described above. Also for other oxides, other compounds that can form oxides by heating may also be used. 

What is claimed is:
 1. A microwave dielectric ceramic composition consisting essentially of, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ wherein (0.925≦x≦0.950), to which 3 to 9 parts by weight of ZnO is added per 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃.
 2. A microwave dielectric ceramic composition as defined in claim 1, wherein the addition amount of ZnO is 5 to 7 parts by weight.
 3. A microwave dielectric ceramic composition as defined in claim 1 or 2, which has a Qu value in the range of 3800 to 4400 at 6 GHz, a temperature coefficient of the resonance frequency in the range of -10 to +10 ppm/°C. and relative dielectric constant in the range of 20 to
 22. 4. A microwave dielectric ceramic composition consisting essentially of, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ wherein (0.923≦x≦0.940), to which 2 to 4 parts by weight of Ta₂ O₅ is added per 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃.
 5. A microwave dielectric ceramic composition as defined in claim 4, wherein x is within a range of 0.927 to 0.935.
 6. A microwave dielectric ceramic composition as defined in claim 4 or 5, which has a Qu value in the range of 3800 to 4400 at 6 GHz, a temperature coefficient of the resonance frequency in the range of -10 to +8 ppm/°C. and relative dielectric constant in the range of 19 to
 22. 7. A microwave dielectric ceramic composition consisting essentially of, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ wherein (0.925≦x≦0.940), to which 1 to 6 parts by weight of Nb₂ O₅ is added per 100 parts by weight of xMTiO₃ ·(1-x)CaTiO₃.
 8. A microwave dielectric ceramic composition as defined in claim 7, wherein the addition amount of Nb₂ O₅ is 1 to 4 parts by weight.
 9. A microwave dielectric ceramic composition as defined in claim 7 or 8, which has a Qu value in the range of 3900 to 4600 at 6 GHz, a temperature coefficient of the resonance frequency in the range of -10 to +8 ppm/°C. and relative dielectric constant in the rage of 20 to
 22. 10. A microwave dielectric ceramic composition consisting essentially of, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ wherein (0.93≦x≦0.95, to which 0.1 to 6 parts by weight of MnO₂ is added per 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃.
 11. A microwave dielectric ceramic composition as defined in claim 10, wherein the addition amount of MnO₂ is 3 to 6 parts by weight.
 12. A microwave dielectric ceramic composition as defined in claim 10 or 11, which has a Qu value in the range of 3000 to 4100 at 6 GHz, a temperature coefficient of the resonance frequency in the range of -5 to +5 ppm/°C. and relative dielectric constant in the range of 19 to
 21. 13. A microwave dielectric ceramic composition consisting essentially of, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ wherein (0.93≦x≦0.95), to which 3 to 12 parts by weight of Al₂ O₃ is added per 100 parts by weight of xMTiO₃ ·(1-x)CaTiO₃.
 14. A microwave dielectric ceramic composition as defined in claim 13, wherein the addition amount of Al₂ O₃ is 3 to 9 parts by weight.
 15. A microwave dielectric ceramic composition as defined in claim 13 or 14, which has a Qu value in the range of 3300 to 3800 at 6 GHz, a temperature coefficient of the resonance frequency in the range of -5 to +3 ppm/°C. and relative dielectric constant in the range of 18 to
 21. 16. A microwave dielectric ceramic composition consisting essentially of, as the main ingredient, a composition represented by xMgTiO₃ ·(1-x)CaTiO₃ wherein (0.93≦x≦0.95), to which 3 to 12 parts by weight of Co₂ O₃ is added per 100 parts by weight of xMgTiO₃ ·(1-x)CaTiO₃.
 17. A microwave dielectric ceramic composition as defined in claim 16, wherein the addition amount of Co₂ O₃ is 3 to 9 parts by weight.
 18. A microwave dielectric ceramic composition as defined in claim 16 or 17, which has a Qu value in the range of 3700 to 4200 at 6 GHz, a temperature coefficient of the resonance frequency in the range of -5 to +2 ppm/°C. and relative dielectric constant in the range of 18 to
 22. 